MX2008012137A - Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides. - Google Patents
Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides.Info
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- MX2008012137A MX2008012137A MX2008012137A MX2008012137A MX2008012137A MX 2008012137 A MX2008012137 A MX 2008012137A MX 2008012137 A MX2008012137 A MX 2008012137A MX 2008012137 A MX2008012137 A MX 2008012137A MX 2008012137 A MX2008012137 A MX 2008012137A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/325—Carbamic acids; Thiocarbamic acids; Anhydrides or salts thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
- A61K31/425—Thiazoles
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31989—Of wood
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- Engineering & Computer Science (AREA)
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- Agronomy & Crop Science (AREA)
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Abstract
A stable, aqueous suspension concentrate which includes a solid polymeric dispersant comprising one or more anionic polymeric dispersing agents, optionally a co-dispersant which preferably is a homopolymer and/or a copolymer of a heterocyclic vinyl lactam, preferably in a wt. ratio of 0.1:1 to 1 :0.1 , a UV-labile, water-insoluble biocide active, and a UV-blocker or UV-absorber to stabilize said active upon storage and/or exposure to sunlight or UV radiation.
Description
CONCENTRATE IN STABLE AQUEOUS SUSPENSION FOR THE SUPPLY OF INSOLUBLE BIOCIDES IN WATER LABILES TO UV RAYS
FIELD OF THE INVENTION This invention relates to delivery systems for active chemical compounds insoluble in water, and, more particularly, to concentrates in stable aqueous suspension of an active concentrate biocidal insoluble in water, labile to UV rays to stabilize these active against the effects of the degradation of sunlight and UV radiation.
BACKGROUND OF THE INVENTION Numerous systems and formulations have been proposed to provide aqueous dispersions of biocidal active compounds substantially water insoluble such as iodopropargyl butyl carbamate (IPBC). For example, Pat. U.S. No. 6,506,794 describes an aqueous dispersion of halopropargyl compounds and a partially hydrolyzed polyvinyl alcohol. However, these active dispersions are very susceptible to degradation with storage and / or exposure to UV radiation. In particular, the decomposition of IPBC usually results in the formulation of a yellow or brown by-product. In this way the compositions will be insoluble for the use of certain systems in need of protection. Ref .: 196582 antimicrobial particularly white water-based paints. Different methods and compositions have been described for stabilizing biocide compositions containing IPBC, for example, using UV absorbers and / or organic epoxides in a liquid carrier, such as Pat. U.S. Nos. 4,276,211; 4,552,885; 5,938,825; 6,059,991 and 6,140,370. Pat. U.S. No. 6,616,740 teaches the use of different glycol vehicles for the stabilization of IPBC. However, none of these descriptions provides a stable IPBC composition as an aqueous dispersion free of yellowing upon exposure to UV radiation. The U.S. Patent No. 6,156,803 discloses the use of partially neutralized maleic acid-alkyl vinyl ether ester copolymer as a dispersing agent for agriculturally active chemicals insoluble in water. U.S. Patent Application published US 2004/0024099 Al discloses an aqueous suspension concentrate for water-insoluble chemical compounds comprising a mixture of an anionic polymeric suspension agent and a homo- and / or co-polymer of a heterocyclic vinyl lactam. Accordingly, it is an object of this invention to provide a stable, aqueous suspension concentrate of a biocidal UV-active active for the delivery of this active compound in stabilized form in formulations and on substrates.
A particular object in the present is to provide these stable concentrates which do not substantially undergo degradation or coloration with storage and / or exposure to sunlight or UV radiation while retaining their bioactivity.
BRIEF DESCRIPTION OF THE INVENTION What is disclosed herein is a stable, aqueous suspension concentrate that includes a polymeric dispersing agent comprising one or more polymeric anionic dispersing agents, optionally a complementary dispersing agent which is preferably a homopolymer and / or copolymer of a heterocyclic vinyl lactam, preferably with a weight ratio of 0.1: 1 to 1: 0.1, respectively, a water-insoluble biocide, labile to UV rays and a UV-blocking or UV-absorber to stabilize the active compound with storage and / or exposure to sunlight or UV radiation. Preferably the stable, aqueous suspension concentrate includes a biocide which is a fungicide or preservative. More preferably the biocide is a halopropargyl compound, an isothiazolone or triazole, a phthalamide, carbamate benzimidazole or tetrachloroisophthalonitrile; more in particular, iodopropargyl butyl carbamate (IPBC), benzisothiazolone (BIT), propiconazole,
N (trichloromethylthio) phthalimide, methyl benzyl-2-yl carbamate or tetrachloroisophthalonitrile. The suitable UV absorber or blocker is titanium dioxide, zinc oxide, stilbenes, or minerals that block UV rays and mixtures of these. The UV absorbers may be aromatic or aliphatic acid esters with appropriate substituents, aromatic ketones, triazines, which are usually commercially available. In one embodiment of the invention, the stable aqueous suspension concentrate includes a complementary dispersing agent comprising a homopolymer or copolymer of vinyl pyrrolidone, and an anionic dispersing agent which is an ionic derivative of maleic acid-methyl ester vinyl ether. A feature of the invention is that the suspension concentrate exhibits essentially no gradation with storage at 50 ° C for 30 days, and substantially no discoloration or yellowing upon exposure to sunlight or UV radiation. The invention herein further comprises a composition that includes a stable aqueous suspension concentrate, e.g., a paint composition.; or a coating composition, construction material such as concrete, bricks, asphalt, splinting, metals and the like; or a composition for personal care. Another feature of the invention is the provision of an article comprising a substrate coated with a suspension concentrate described alone; eg, an article where the substrate is wood.
DETAILED DESCRIPTION OF THE INVENTION The main dispersing agent in the present solid polymeric dispersion agent composition of the invention is an anionic polymeric dispersing agent such as the sodium salt of maleic acid ester / alkyl vinyl ether copolymer (Easy-Sperse ®) (ISP), a lignosulfate or metallic salt thereof, eg, POLYFON® or REAX® (Weastvaco); a sulfonated naphthalene / formaldehyde condensate, e.g., MORWET® (Witco); UFOXANE® or ARESPERSE® (lignotech); an alpha-olefin / maleic acid copolymer, a high molecular weight block copolymer with pigment-like groups, eg, DISPERBYCK 190 (BYK Chemie) or a polyacrylate, which is capable of dispersing hydrophobic compounds in water and mixtures of these. Desirably the monomer of the anionic polymer contains 1-4 anionic sites per mole of repeating units. The optional complementary dispersing agent in the composition of the invention is a vinyl lactam which is suitable for the homopolymer of vinyl pyrrolidone or vinyl caprolactam either optionally substituted in the ring or in the vinyl group with a lower alkyl (Ci to C4 alkyl) ), or a mixture of these homopolymers. Alternatively, the complementary dispersing agent can be a copolymer of vinyl pyrrolidone and / or vinyl caprolactam, eg, vinyl pyrrolidone / vinyl caprolactam copolymer, vinyl acetate / vinyl pyrrolidone, vinyl pyrrolidone / acrylic acid, vinyl pyrrolidone / acrylate , vinyl pyrrolidone and butane, or a vinyl pyrrolidone and a C14-C24 alpha-olefin. The vinyl lactam supplemental dispersing agent generally has an average molecular weight between about 5,000 and about 100,000 consistent with a K-Fikeritscher value of from about 10 to about 120. The complementary dispersing agent may be a clay selected from silicates of origin natural, acicular clay, bentonite, diatomaceous earth, and montmorillonite. In the solid dispersion agent mixture, the lactam polymer can be wound around and coated with at least a portion of a water insoluble active ingredient thereby reducing its surface hydrophobicity while retaining the intrinsic hydrophobic character of the insoluble active compound. The lactam coating can also be associated with anions of the main dispersing agent to provide an improved stability composition and allows high load active compositions to disperse hydrophobic species which can not be suspended. The use of the lactam polymer dispersion agent in addition in the solid mixture of the invention allows the use of a lower concentration of the primary anionic polymeric dispersing agent component which reduces the irritant and / or foaming properties. Also the presence of the lactam polymer in the solid mixture allows the use of different incompatible anionic polymeric dispersing agents. The active compound of the compositions of the invention is a particle, a biocidal compound labile to UV rays substantially insoluble in water, or a hydrophobic compound or mixture of these compounds, and is preferably a biocide such as a halopropargyl compound, an isothiazolone, an triazole, a phthalimide, a benzimidazole carbamate, a tetrachloroisophthalonitrile and the like. Some of these biocidal compounds usually exhibit significant degradation with certain storage conditions and / or exposure to sunlight or UV radiation accompanied by discoloration when used in these products such as paint, wood or personal care formulations. . The term "substantially insoluble" means that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practically useful in a sprayer or pointed end used without some modification either to increase its solubility or dispersion in water , as well as increasing the bioavailability of the compound or avoiding the use of excessively large volumes of solvent. Compounds that have low water solubility include those that have a solubility of less than 1 gram per 100 grams of water at room temperature conditions. Typical "substantially insoluble" biocides include: iodopropargyl butyl carbamate (IPBC), benzisothiazolone (BIT), propiconazole, N (trichloromethylthio) phthalimide, methyl benzimidazol-2-yl carbamate, tetrachloroisofalonitrile, 2-n-octyl-3-isothiazolone, dibromonitriloproprionamide (DBNPA), 2- (thiocyanomethylthio) benzotriazole (TCMTB), tebuconazole, tributyl tin benzoate, parabens, 2,5-dimethyl-N-cyclohexyl-N-methoxy-3-furan carboxamide, 5-ethoxy-3-trichloromethyl-1,2,4 thiadiazole, 3,4-dichlorobenzoate 3 - (2-methyl piperidin) propyl, N, N '- (1,4-piperazindiyl bis (2, 2, 2-trichloro) ethylidene) bis formamide, tetramethyl thiuram bisulphide, O-ethyl-S, S-diphenyl- dithiophosphate, 5,10-dihydro-5,10-dioxo-naphtho (2,3,9) -p-dithiin-2,3-dicarbonitrile, OI-2- [(4-chlorophenyl) ethyl] -a- (1, 1-dimethyl ethyl) -l H-1,2,4-triazole-l-ethanol 3- (3,4-dichlorophenyl) -1,1-dimethylurea, N-tridecyl-2,6-dimethylmorpholine and 4-N-dodecyl -2, β-dimethylmorpholine. The term "UV-labile" means for all practical purposes, the active ingredient is susceptible to the absorption of any part of natural sunlight or exposed to artificial light. In general, any ingredient containing unsaturated radicals, especially with conjugation and aromatic or heterocyclic component, will be subject to the absorption of this radiation, which can eventually lead to a degradation with color change or loss of activity. In this invention, the term "UV blocking, UV absorber" includes those compounds that will cause a considerable change of an appropriate active portion of the radiation spectral component. The present invention provides a suspension concentrate that is environmentally suitable, and free of conventional organic solvents and emulsifiers. The aqueous suspension concentrate herein can be formulated with multiple active ingredients to improve its spectrum of activity. The concentrate is easily diluted with water. A high salt content in the groundwater of the field will not affect its stability with dilution. The suspension concentrate can be easily made by standard methods, as described below: The commercial product Eary-Sperse® (International Specialty Products Inc.) is suitably employed as the anionic polymeric dispersing agent in the solid composition of the invention. Easy-Sperse® is the partially neutralized aqueous solution of copolymer (ethyl / butyl) ester-half methyl vinyl ether / maleic acid having a solids content of approximately 25% and a viscosity of approximately 6,000 cps. The optional complementary dispersing agent in the composition is suitably an aqueous solution of polyvinyl pyrrolidone (20-40% solids). A solution / slurry of both the main and complementary dispersing agent is provided with a weight ratio of these ingredients from 0.1: 1 to 1: 0.1, respectively, preferably 1: 0.5 to 1: 5, and, more preferably 1: 1. to 1: 4. The solution / slurry can be diluted with water, if necessary to produce a viscosity particularly suitable for spray drying, eg, 3,000 to 6,000 cps. The solution / slurry is then spray dried appropriately with an inlet temperature of about 66-252 ° C (300-480 ° F). The product of the spray-drying process is a concentrated polymer dispersion agent suitable for labile UV-light supply, the biocidal activity insoluble to water. However, if both the primary and complementary dispersion agents are commercially available as solids, then only the simple granulation of the ingredients is required to obtain the desired solid concentrate. The active material can then be added in a suitable amount and processed, if desired, to active compounds sensitive to water, under anhydrous conditions, and made in solid supply systems such as wettable powders, water dispersible granules and tablets. If desired, the solid form can be used in an aqueous medium with dilution water, in an aqueous or suspension formulation. The formulation can also be coated on hydrophobic surfaces, or printed on sheets. The products of the invention are advantageous from the commercial point of view for the following reasons. In particular, the suspension concentrate exhibits essentially no degradation upon storage at 50 ° C for 30 days, and substantially if discoloration or yellowing upon exposure to sunlight or UV radiation. The solid composition of the invention can also be prepared efficiently by simple homogenization and wet milling of the components or by extrusion. The composition can be diluted with a desired amount of water by mixing with a high speed mixer for a period of about 30 minutes to 1 hour. The composition of the present invention can incorporate up to 90% of the active material in its mixture while retaining its stability for at least 1 year or more. In the dilution of the active compound can have a concentration of 10 ppm to 50% in the diluted mixture while retaining stability of the suspension for 4 hours or more. The combination of the anionic dispersing agent with the lactam polymer has a synergistic suspension effect in that the dispersion ability of the sum of either the component alone is markedly exceeded. Having generally described the invention, the reference had the following examples illustrating preferred embodiments and comparisons of the present concentrate or formulation with those of the prior art.
EXAMPLE 1 Preparation of Concentrate of Polymeric Dispersing Agent of the Invention 72 g of Easy-Sperse® solution (24.8% solids) were mixed with 176 g of PVP K-30 (30.5% solids), then homogenized at room temperature for 1 hour and concentrated in a protective hood overnight at room temperature followed by drying in a vacuum oven (<10 mm Hg) at 80 ° C for 2 hours. The resulting solid product had a Tg of 159 ° C and < 1% moisture absorbed and a weight ratio of Easy-Sperse® to PVP of 1: 3.
EXAMPLE 2 Preparation of Concentrate of Polymeric Dispersion Agent by Spray Drying 240 Kg of Easy-Sperse® solution (26% solids) and 720 Kg of PVP K-30 (36.6% solids) were mixed and heated to 49 ° C ( 120 ° F) and then diluted with 272.4 kg (600 lbs) of water. The resulting solution was fed into a commercial spray dryer with an inlet temperature of 129 ° C (265 ° F). A solid was obtained in the form of a powder which was passed through a 20 mesh screen. 317.8 Kg (700 lbs) of dry material with 7% of total absorbed moisture was obtained. The weight ratio of Easy-Sperse® to PVP was 1: 4.
EXAMPLE 3 Examples 1 and 2 were repeated with a weight ratio of 1: 1. Similar results were obtained.
EXAMPLE 4 Examples 1 and 2 were repeated with a weight ratio of 1: 2. Similar results were obtained.
EXAMPLE 5 Example 1 was repeated with Morwet® D-425 solid in place of an Easy-Sperse® solution, and a PVP solution to produce a 1: 1 ratio of solid.
EXAMPLE 6 Example 5 was repeated with a weight ratio of 1: 3 with similar results.
EXAMPLE 7 Example 5 was repeated with Reax® 100M solid instead of Morwet® D-425 with similar results.
EXAMPLE 8 Example 6 was repeated with Reax® 100M solid instead of Morwet® D-425 with similar results.
EXAMPLE 9 Mixture of Solid Dispersion Agent and Biocidal Active Compound 700 g of commercial IPBC active compound were mixed with 80 g of the polymeric dispersing agent of Example 2 and 220 g of commercially available titanium dioxide in a V-blender. This solid premix was used to formulate wettable powders, suspension concentrates, water dispersible granules and tablets of the active compound.
EXAMPLE 10 700 g of commercially active compound BIT were mixed with 80 g of the polymeric dispersing agent of Example 2 and 220 g of commercially available titanium dioxide in a V-blender. This solid premix was used to formulate wettable powders, suspension concentrates, water dispersible granules and tablets of the active compound.
EXAMPLE 11 300 g of commercial IPBC active compound were mixed with 70 g of dispersion agent / polymeric binder composition of Example 6 and 100 g of commercially available titanium dioxide in a V-blender. This filler was used to produce extruded granules and tablets.
EXAMPLE 12 100 g of the filler of Example 11 were formulated in a portion by kneading with water (10-20 g) and extruded in a table top extruder at maximum speed. The extrudate was dried in an oven at 70 ° C for a period of 8 hours. The extrudate was dispersed in water with an IPBC level concentration from 0.1% to 2.0%.
EXAMPLE 13 50 g of the extrudate of Example 12 were mixed with 1.5 g of cross-linked polyvinyl pyrrolidone (Polyclar® ATF) and different tablets were formulated by compressing the powder in a laboratory tablet press with a pressure of 2.5 tons. Each tablet weighed approximately 3 g, which contains about 1.86 g of IPBC. Aqueous suspensions were made by dispersing each tablet in 186 g of water with medium agitation for about 10 minutes, to produce 1% IPBC suspension.
EXAMPLE 14 The following briefly describes the process used to prepare the suspension concentrates of biocides shown in the following Examples 15A to 15D. Biocidal suspension concentrate compositions with suitable and preferred weight ranges prepared in this manner include: Active ingredient: 5-50%; preferred range 10-40%; polymer dispersion agent; 0.2-8%, preferred: 1-5%; UV blocking agent: 0.2-20%, preferred: 2-10%; thickener: 0.05-0.4%; preferred: 0.1-0.3%; Wetting agent: 0-1.0%, preferred: 0-0.5%; antifoam: 0.05-0.4%, preferred: 0.1-0.3%; conservative: 0-0.5% preferred 0-0.2% and 100% water.
General procedure: In a vessel with Cowles mixer approximately 80% of the required water was added, followed by the wetting agent, dispersing agent, UV-blocking agent, and the active ingredient. It was mixed at 500 rpm for 30 minutes. The putant and thickener was added to the above mixture and the remaining water, and mixed at 2000 rpm for an additional 30 minutes. The load was pumped into a basket mill and ground to the desired particle size, usually about 10 micrometers in average particle size (a Hegman ratio between 6 and 7).
Thickeners are usually available water soluble polymers that impart high viscosity when added at very low concentrations, such as natural gums, carbohydrates such as Kelzan®, synthetic polymers such as Carbopol® (po 1 i a c r i 1 a t). Wetting agents are used to reduce friction during high-speed grinding, usually low foaming organic liquids with a low dynamic surface tension, eg, Surfynol® series or N-octyl pyrrolidone. The preservatives used are commercially available registered organic compounds capable of controlling biological growth in aqueous media for a reasonable storage period of about 1-5 years, eg, Nuosept® series, Kathon®, Proxel® and the like.
EXAMPLE 15A 1 Kg of an aqueous suspension concentrate was prepared using approximately 200 g of commercially available IPBC, by the general procedure described in Example 14, 220 g of IPBC were mixed with 25 g of Easy-sperse® P polymeric dispersion agent. 20 and 600 g of deionized water. The load was charged to a low speed mixer followed by high speed mixing over a period of 30 minutes. During the mixing process, 1.0 g of Surfinol® 104 E was added along with 1.0 g of Sag 30. The filler was processed as in Example 14. The suspension concentrate was then mixed with a stock solution of 122 g of Kelzan® at 1% prepared separately, followed by the addition of the remaining amount of water (53 g) to make a 22% IPBC concentrate.
EXAMPLE 15B Example 15A was repeated except that 50 g of zinc oxide were included in the initial solid mixture and 3 g of complement water was used in the end instead of 53 g of water.
EXAMPLE 15C Example 15B was repeated except that titanium dioxide was used instead of zinc oxide.
EXAMPLE 15D Example 15C was repeated using 400 g of IPBC instead of 200 g and 40 g of Easy-Spear® P 20 instead of 25 g and the initial water of 400 g instead of 600 g and the water of complement was 23 g .
EXAMPLE 15E Example 15C was repeated except that Disperbyck 190 was used instead of Easy-Sperse. The suspension concentrates described in Example 15 A, 15B, and 15 C were evaluated in their yellowness with exposure to UV light. The same results were shown in Example 16. Examples 15 C and 15 E were evaluated for accelerated storage stability. These results are shown in Example 17. Example 15 D was evaluated as an additive in paint. These results were shown in Example 18.
EXAMPLE 16 TABLE 1 Yellowing with Exposure to UV Light
"+" = yellowing; "A" = no yellowing EXAMPLE 17 Stability of the IPBC in Aqueous Suspension Concentrate The IPBC dispersion described in Example 15 C and 15E was thermally aged for 30 days at 50 ° C. The resulting IPBC levels were determined by reverse phase CLAR. The levels of IPBC detected in Sample 15C were 21.54 ± 0.06, which were the same levels as the sample analyzed at time zero, immediately after the preparation of the concentrate in suspension. The levels of IPBC detected in sample 15E were 20.34 + 0.2%, which is the same level of the sample analyzed at time zero. The efficacy of 40% of the suspension concentrate of IPBC in Example 15 Dwas compared with that of a commercial IPBC formulation followed by ASTM D5590 entitled "Determining the Resistance of Paint Films and Related Coatings Toh Fangal Defacement by Accelerated Four Week Agar Píate". The results are shown in Table 2. The growth ratios were taken every 7 days, on a scale of "0" to "10", where "0" corresponds to the complete absence of fungal growth and "10" corresponds to the coverage completely with the fungus. The mixed inoculum contained in the fungus Aspergillus niger and Penicillium funiculosum.
TABLE 2 Efficacy of IBPC Aqueous Suspension Concentrate
EXAMPLE 19 1 Kg of an aqueous suspension concentrate was prepared with BIT following the procedure of Example 15C.
EXAMPLE 20 The efficiency of the BIT dispersion described in Example 19 was compared with that of the commercial BIT formulation of similar strength following the procedure ASTM D2574 entitled "Resistance of Emulsion Paints in the Container Toh Attack by Microorganisms". The results are shown in Table 3. Growth rates were taken on day 1, 2, 3 and 6 after each bacterial challenge on an "O" to "4" scale; where "0" corresponds to no growth, "1" is less than 10 cfu / ml, "2" is 11-100 cfu / ml; "3" is 101-1,000 cfu / ml and "4" is greater than 1,000 cfu / ml. The mixed bacterial inoculum consisted of Pseudomonas aeruginosa, Enterobacter cloacae, Bacillus subtilis, Bacillus megaterium and Bacillus licheniformis. The final challenge I concentration was 1.52x106 cfu / ml and for challenge II, 1.56x107 cfu / ml.
TABLE 3 Effectiveness of BIT Aqueous Suspension Concentrate
EXAMPLE 21 Example 15 was repeated using propiconazole instead of IPBC. Similar results were obtained.
EXAMPLE 22 Example 19 was repeated using a combination of IPBC and propiconazole with a weight ratio of 1: 2. Similar results were obtained.
EXAMPLE 23 Example 15 was repeated using Folpet instead of IPBC. Similar results were obtained.
EXAMPLE 24 Example 15 was repeated using chlorothalonil. Similar results were obtained. Since the invention has been described with particular reference to certain embodiments thereof, it is understood that changes and modifications can be made which are within the skill of the art. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Claims (1)
- CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Concentrate in stable aqueous suspension including a solid polymeric dispersing agent, characterized in that it comprises one or more polymeric anionic dispersing agents, an active biocidal compound insoluble in water, labile to UV rays and a UV blocker or UV absorber to stabilize the active compound with storage and / or exposure to sunlight or UV radiation. 2. Concentrate in stable aqueous suspension according to claim 1, characterized in that the solid polymer dispersion agent further comprises a complementary dispersing agent. 3. Concentrate in stable aqueous suspension according to claim 2, characterized in that the complementary dispersing agent is a homopolymer and / or copolymer of a heterocyclic vinyl lactam. . Concentrated in stable aqueous suspension according to claim 2, characterized in that the anionic polymeric dispersing agent and the complementary dispersing agent are present with a weight ratio of 0.1: 1 to 1: 0.1. 5. Concentrated in stable aqueous suspension according to claim 1, characterized in that the anionic polymeric dispersing agent is selected from the group consisting of a copolymer of the sodium salt of the ester, alkyl vinyl ether / maleic acid, a salt of lignosulphate or metal of this , a sulfonated naphthalene / formaldehyde condensate, an alpha olefin / maleic acid copolymer, a polyacrylate and mixtures thereof. 6. Concentrate in stable aqueous suspension according to claim 1, characterized in that the biocide is a fungicide. 7. Concentrate in stable aqueous suspension according to claim 6, characterized in that the biocide is a preservative. 8. Concentrate in stable aqueous suspension according to claim 6, characterized in that the fungicide is a halopropargyl compound, an isothiazolone, a triazole, a phthalimide, a benzimidazole carbamate or tetrachloroisophthalonitrile. 9. Concentrate in stable aqueous suspension according to claim 1, characterized in that the active biocidal compound is a iodopropargyl butyl carbamate. 10. Concentrate in stable aqueous suspension according to claim 7, characterized in that the preservative is benzisothiazolone. 11. Concentrate in stable aqueous suspension according to claim 1, characterized in that the UV-blocking agent is titanium dioxide, zinc oxide, a stilbene, a mineral that blocks UV rays and mixtures thereof. 12. Concentrate in stable aqueous suspension according to claim 2, characterized in that the complementary dispersing agent comprises a homopolymer or copolymer of vinyl pyrrolidone and an ionic derivative of ester methyl vinyl ether / maleic acid ester. 13. Concentrate in stable aqueous suspension according to claim 2, characterized in that the complementary dispersing agent is clay selected from naturally occurring silicates, acicular clay, bentonite, diatomaceous earth, and Montmorillonite. 14. Concentrate in stable aqueous suspension according to claim 1, characterized in that it exhibits essentially no storage degradation at 50 ° C for 30 days, and substantially no discoloration or yellowing upon exposure of sunlight or UV radiation. 15. Composition, characterized in that it includes the concentrate according to claim 1. 16. Paint, characterized in that it includes the concentrate according to claim 1. 17. Composition for personal care characterized in that it includes the concentrate according to claim 1 18. Article, characterized in that it comprises a substrate coated with the suspension concentrate according to claim 1. 19. Article according to claim 18, characterized in that the substrate is wood. 20. Stable, water-dispersible solid comprising a solid polymeric dispersing agent, characterized in that it comprises one or more anionic polymeric dispersing agents, a water-insoluble, biocidal active compound, UV-labile and a UV-blocking agent or absorber. of UV rays to stabilize the active compound with storage and / or exposure to sunlight or UV radiation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11/388,553 US20070224135A1 (en) | 2006-03-24 | 2006-03-24 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
PCT/US2007/007432 WO2007112091A2 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides |
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MX2008012137A true MX2008012137A (en) | 2008-10-03 |
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MX2008012137A MX2008012137A (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides. |
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US (2) | US20070224135A1 (en) |
EP (2) | EP3023089A1 (en) |
JP (1) | JP5306177B2 (en) |
KR (1) | KR20090008262A (en) |
CN (1) | CN101505600A (en) |
AU (1) | AU2007230909B9 (en) |
BR (1) | BRPI0709118B1 (en) |
CA (1) | CA2646280C (en) |
MX (1) | MX2008012137A (en) |
WO (1) | WO2007112091A2 (en) |
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US20130045241A1 (en) * | 2009-12-07 | 2013-02-21 | Isp Investments Inc. | Stabilized aqueous dispersion of folpet analogues, method of preparing the same and composition thereof |
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CN104114023A (en) * | 2011-12-15 | 2014-10-22 | 陶氏益农公司 | High load aqueous suspension concentrate of an active ingredient |
US8927619B2 (en) * | 2011-12-21 | 2015-01-06 | Jorg Thomas Wilken | Color-stabilized iodopropynyl butylcarbamate |
CN104080333B (en) | 2011-12-22 | 2017-06-23 | 维弗作物保护公司 | Strobilurins preparation |
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CN103392735A (en) * | 2013-06-30 | 2013-11-20 | 广东中迅农科股份有限公司 | Pesticide suspending agent containing inorganic nano-material and preparation method thereof |
US20150240495A1 (en) | 2014-02-21 | 2015-08-27 | Owens Corning Intellectual Capital, Llc | Shingles with increased hydrophobicity |
US9756859B1 (en) | 2016-08-11 | 2017-09-12 | Troy Technology Ii, Inc. | Stable aqueous dispersions of biocides |
WO2018185710A1 (en) * | 2017-04-07 | 2018-10-11 | Sabic Global Technologies B.V. | Durable surface hardened coating or overcoating for protecting plants from pests |
US11517013B2 (en) | 2017-08-25 | 2022-12-06 | Vive Crop Protection Inc. | Multi-component, soil-applied, pesticidal compositions |
US10865565B2 (en) | 2018-07-11 | 2020-12-15 | Owens Coming Intellectual Capital, LLC | Shingles with increased hydrophobicity |
BR112021015944A2 (en) * | 2019-02-15 | 2021-12-07 | Whiteley Corp Pty Ltd | Improved endoscope disinfectant |
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-
2006
- 2006-03-24 US US11/388,553 patent/US20070224135A1/en not_active Abandoned
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2007
- 2007-03-26 CA CA2646280A patent/CA2646280C/en not_active Expired - Fee Related
- 2007-03-26 BR BRPI0709118A patent/BRPI0709118B1/en not_active IP Right Cessation
- 2007-03-26 CN CNA2007800106555A patent/CN101505600A/en active Pending
- 2007-03-26 EP EP15199852.3A patent/EP3023089A1/en not_active Withdrawn
- 2007-03-26 WO PCT/US2007/007432 patent/WO2007112091A2/en active Application Filing
- 2007-03-26 EP EP07754009A patent/EP1998739A4/en not_active Withdrawn
- 2007-03-26 JP JP2009501608A patent/JP5306177B2/en not_active Expired - Fee Related
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- 2007-03-26 MX MX2008012137A patent/MX2008012137A/en active IP Right Grant
- 2007-03-26 KR KR1020087025820A patent/KR20090008262A/en not_active Application Discontinuation
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US20070224135A1 (en) | 2007-09-27 |
JP2009533329A (en) | 2009-09-17 |
EP1998739A4 (en) | 2012-10-31 |
BRPI0709118A2 (en) | 2011-06-28 |
AU2007230909B9 (en) | 2014-03-27 |
CA2646280C (en) | 2014-08-05 |
KR20090008262A (en) | 2009-01-21 |
US9044010B2 (en) | 2015-06-02 |
US20110081555A1 (en) | 2011-04-07 |
CN101505600A (en) | 2009-08-12 |
BRPI0709118B1 (en) | 2016-06-14 |
WO2007112091A3 (en) | 2009-04-09 |
EP3023089A1 (en) | 2016-05-25 |
AU2007230909A1 (en) | 2007-10-04 |
WO2007112091A2 (en) | 2007-10-04 |
CA2646280A1 (en) | 2007-10-04 |
JP5306177B2 (en) | 2013-10-02 |
EP1998739A2 (en) | 2008-12-10 |
AU2007230909B2 (en) | 2013-11-07 |
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